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Intra‐ and Intermolecular H···Cl–Ni Bonding Patterns in a Series of Highly Preorganized Dinuclear Nickel(II) Complexes
Author(s) -
Nie FengMei,
Leibeling Guido,
Demeshko Serhiy,
Dechert Sebastian,
Meyer Franc
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600889
Subject(s) - chemistry , nickel , intramolecular force , crystallography , acceptor , ligand (biochemistry) , hydrogen bond , intermolecular force , linkage isomerism , stereochemistry , chelation , dimer , molecule , metal , inorganic chemistry , organic chemistry , biochemistry , physics , receptor , condensed matter physics
Four dinickel complexes [L 1 Ni 2 (μ‐Cl)(Cl) 2 ] · 2CH 3 OH ( 1a ), [L 1 Ni 2 (μ‐Cl)(CH 3 OH)](ClO 4 ) 2 ( 1b ), [L 2 Ni 2 (μ‐Cl)Cl 2 (H 2 O) 2 ] · H 2 O ( 2 ) and [L 3 Ni 2 Cl 2 (CH 3 OH) 2 ]Cl · 2CH 3 OH ( 3 ) were synthesized and structurally characterized. The ligand scaffolds have a central pyrazolato bridge and N‐donor chelate arms that provide two proximate binding pockets for the nickel ions. While the longer ligand side arms in 1a , 1b and 2 induce Ni ··· Ni distances of around 4.0 Å and favour incorporation of a chlorido bridge within the dimetallic pocket, a stretched Ni ··· Ni separation of 4.6 Å with an unusual intramolecular Cl ··· H–O linkage is observed in 3 . Various Cl ··· H–O hydrogen‐bonding motifs are identified in the solid‐state structures of 1 – 3 , where either the H‐donor (MeOH or H 2 O) or the H‐acceptor (chlorido) or both are bound to a nickel ion, and their relative donor–acceptor distances are discussed. Magnetic coupling mediated through the pyrazolato and chlorido bridges is rather weak and antiferromagnetic, but it is even weaker for the Cl ··· H–O linkage. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)